Chemistry of theElementsSecond Edition

N . N . GREENWOOD and A. EARNSHAWSchool of ChemistryUniversity of Leeds, U.K.

AMSTERDAM " BOSTON " HEIDELBERG " LONDON

" NEW YORK " OXFORDPARIS "

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Contents

Preface to the second editionPreface to the first edition

Chapter 1

Origin of the Elements . Isotopes and Atomic Weights

11 .1 Introduction1 .2

Origin of the Universe1 .3

Abundances of the Elements in the Universe1 .4

Stellar Evolution and the Spectral Classes of Stars1 .5

Synthesis of the Elements1 .5 .1

Hydrogen burning1 .5 .2

Helium burning and carbon burning1 .5 .3

The a-process1 .5 .4

The e-process (equilibrium process)1 .5 .5

The s- and r-processes (slow and rapid neutron absorption)1 .5 .6

The p-process (proton capture)1 .5 .7

The x-process1 .6

Atomic Weights1 .6 .1

Uncertainty in atomic weights1 .6 .2

The problem of radioactive elements

Chapter 2

Chemical Periodicity and the Periodic Table2 .1 Introduction2.2

The Electronic Structure of Atoms2.3

Periodic Trends in Properties2 .3 .1

Trends in atomic and physical properties2 .3 .2

Trends in chemical properties2.4

Prediction of New Elements and Compounds

Chapter 3

Hydrogen

323 .1 Introduction3.2

Atomic and Physical Properties of Hydrogen3.2 .1

Isotopes of hydrogen3.2 .2

Ortho- and para-hydrogen3.2 .3

Ionized forms of hydrogen3.3

Preparation, Production and Uses3.3.1 Hydrogen3.3.2 Deuterium3 .3 .3 Tritium

3.4

Chemical Properties and Trends3AI

The coordination chemistry of hydrogen

v

I13599101112121313151618

20202123232729

3234343536383839414344

3 .5

Protonic Acids and Bases3 .6

The Hydrogen Bond3.6 .1

Influence on properties3 .6 .2

Influence on structure3 .6 .3

Strength of hydrogen bonds and theoretical description3 .7

Hydrides of the Elements

485253596164

Chapter 4

Lithium, Sodium, Potassium, Rubidium, Caesium and

68Francium4 .1 Introduction

684.2

The Elements

684.2 .1

Discovery and isolation

684.2.2

Terrestrial abundance and distribution

694.2.3

Production and uses of the metals

714.2.4

Properties of the alkali metals

744.2.5

Chemical reactivity and trends

764.2.6

Solutions in liquid ammonia and other solvents

774.3 Compounds

794.3.1

Introduction : the ionic-bond model

794.3.2

halides and hydrides

824,3.3

Oxides, peroxides, superoxides and suboxides

844.3.4 Hydroxides

864.3.5

Oxoacid salts and other compounds

874.3.6

Coordination chemistry

904.3.7 . Imides, amides and related compounds

994.3.8

Organometallic compounds

102

Chapter 5

Beryllium, Magnesium, Calcium, Strontium, Barium and

107Radium5 .1 Introduction

1075.2

The Elements

1085.2 .1

Terrestrial abundance and distribution

1085.2 .2

Production and uses of the metals

1105.2 .3

Properties of the elements

1115.2 .4

Chemical reactivity and trends

1125.3 Compounds

1135.3 .1 Introduction

1135.3 .2

Hydrides and halides

1155.3 .3

Oxides and hydroxides

1195.3 .4

Oxoacid salts and coordination complexes

1225.3 .5

Organometallic compounds

127Beryllium

127Magnesium

131Calcium, strontium and barium

136

Chapter 6

Boron

1396.1 Introduction

1396.2 Boron

1406.2 .1

Isolation and purification of the element

1406.2.2

Structure of crystalline boron

1416.2 .3

Atomic and physical properties of boron

1446.2.4

Chemical properties

1446.3 Borides

1456.3.1 Introduction

1456.3.2

Preparation and stoichiometry

1466.3 .3

Structures of borides

147

Contents

vii

6.4

Bpranes (Boron Hydrides)

1516.4 .1 Introduction

1516.4.2

Bonding and topology

1576.4.3

Preparation and properties of boranes

1626.4.4

The chemistry of small boranes and their anions (Bt -B4)

1646.4.5

Intermediate-sized boranes and their anions (B5-B9)

1706.4.6

Chemistry of nido-decaborane, BlOH14

1736.4.7

Chemistry of closo-B� H� 2-

1786.5 Carboranes

1816.6 Metallocarboranes

1896.7

Boron Halides

1956.7 .1

Boron trihalides

1956.7 .2

Lower halides of boron

2006.8

Boron-Oxygen Compounds

2036.8 .1

Boron oxides and oxoacids

2036.8.2 Borates

2056.8 .3

Organic compounds containing boron-oxygen bonds

2076.9

Boron-Nitrogen Compounds

2076.10

Other Compounds of Boron

2116.10.1

Compounds with bonds to P, As or Sb

2116.10.2

Compounds with bonds to S, Se and Te

213

Chapter 7

Aluminium, Gallium, Indium and Thallium

2167 .1 Introduction

2167.2

The Elements

2177.2 .1

Terrestrial abundance and distribution

2177.2.2

Preparation and uses of the metals

2197.2.3

Properties of the elements

2227.2 .4

Chemical reactivity and trends

2247.3 Compounds

2277.3 .1

Hydrides and related complexes

2277.3 .2

Halides and halide complexes

233Aluminium trihalides

233Tribalides of gallium, indium and thallium

237Lower halides of gallium, indium and thallium

2407.3 .3

Oxides and hydroxides

2427.3 .4

Ternary and more complex oxide phases

247Spinels and related compounds

247Sodium-ß-alumina and related phases

249Tricalcium aluminate, Ca3A1206

2517.3 .5

Other inorganic compounds

252Chalcogenides

252Compounds with bonds to N, P, As, Sb or Bi

255Some unusual stereochemistries

2567.3.6

Organometallic compounds

257Organoaluminium compounds

258Organometallic compounds of Ga, In and TI

262Al-N heterocycles and clusters

265

Chapter 8

Carbon

2688 .1 Introduction

2688.2 Carbon

2698.2.1

Terrestrial abundance and distribution

2698.2.2

Allotropic forms

2748.2.3

Atomic and physical properties

2768.2.4 Fullerenes

278Structure of the fullerenes

280Other molecular allotropes of carbon

282Chemistry of the fullerenes

282Reduction of fullerenes to fullerides

285

Viii

Contents

Chapter 9

Silicon

328

Chapter 10

Germanium, Tin and Lead

367

Chapter 11

Nitrogen

Addition reactions

286Heteroatom fullerene-type clusters

287Encapsulation of metal atoms by fullerene clusters

2888.2 .5

Chemical properties of carbon

2898.3

Graphite Intercalation Compounds

2938.4 Carbides

296Metallocarbohedrenes (met-cars)

3008.5

Hydrides, Halides and Oxohalides

3018.6

Oxides and Carbonates

3058.7

Chalcogenides and Related Compounds

3138.8

Cyanides and Other Carbon-Nitrogen Compounds

3198.9

Organometallic Compounds

326

9.1 Introduction

3289.2 Silicon

3299.2 .1

Occurrence and distribution

3299.2.2

Isolation, production and industrial uses

3309.2 .3

Atomic and physical properties

3309.2.4

Chemical properties

3319.3 Compounds

3359.3 .1 Silicides

3359.3.2

Silicon hydrides (silanes)

3379.3 .3

Silicon halides and related complexes

3409.3.4

Silica and silicic acids

3429.3 .5

Silicate minerals

347Silicates with discrete units

347Silicates with chain or ribbon structures

349Silicates with layer structures

349Silicates with framework structures

3549.3.6

Other inorganic compounds of silicon

3599.3 .7

Organosilicon compounds and silicones

361

10.1 Introduction

36710.2

The Elements

36810.2.1

Terrestrial abundance and distribution

36810.2.2

Production and uses of the elements

36910.2.3

Properties of the elements

37110.2.4

Chemical reactivity and group trends

37310.3 Compounds

37410.3 .1

Hydrides and hydrohalides

37410.3 .2

Halides and related complexes

375Germanium halides

376Tin halides

377Lead halides

38110.3 .3

Oxides and hydroxides

38210.3 .4

Derivatives of oxoacids

38710.3 .5

Other inorganic compounds

38910.3 .6

Metal-metal bonds and clusters

39110.3.7

Organometallic compounds

396Germanium

396Tin

399Lead

404

11.1 Introduction406406

11 .2

The Element

40711 .2 .1

Abundance and distribution

40711 .2 .2

Production and uses of nitrogen

40911 .2 .3

Atomic and physical properties

41111 .2 .4

Chemical reactivity

41211 .3 Compounds

41611 .3 .1

Nitrides, azides and nitrido complexes

41711 .3 .2

Ammonia and ammonium salts

420Liquid ammonia as a solvent

42411 .3 .3

Other hydrides of nitrogen

426Hydrazine

427Hydroxylamine

431Hydrogen azide

43211 .3 .4

Thermodynamic relations between N-containing species

43411 .3 .5

Nitrogen halides and related compounds

43811 .3 .6

Oxides of nitrogen

443Nitrous oxide, N20

443Nitric oxide, NO

445Dinitrogen trioxide, N203

454Nitrogen dioxide, N02, and dinitrogen tetroxide, N204

455Dinitrogen pentoxide, N205, and nitrogen trioxide, N03

45811 .3 .7

Oxoacids, oxoanions and oxoacid salts of nitrogen

459Hyponitrous acid and hyponitrites

459Nitrous acid and nitrites

461Nitric acid and nitrates

465Orthonitrates, M3N04

471

Chapter 12

Phosphorus

473

12 .1 Introduction

47312.2

The Element

47512.2 .1

Abundance and distribution

47512.2.2

Production and uses of elemental phosphorus

47912.2 .3

Allotropes of phosphorus

47912.2.4

Atomic and physical properties

48212.2 .5

Chemical reactivity and stereochemistry

48312.3 Compounds

48912.3 .1 Phosphides

48912.3 .2

Phosphine and related compounds

49212.3 .3

Phosphorus halides

495Phosphorus trihalides

495Diphosphorus tetrahalides and other lower halides of phosphorus

497Phosphorus pentahalides

498Pseudohalides of phosphorus(III)

50112.3 .4

Oxohalides and thiohalides of phosphorus

50112.3 .5

Phosphorus oxides, sulfides, selenides and related compounds

503Oxides

503Sulfides

506Oxosulfides

51012.3 .6

Oxoacids of phosphorus and their salts

510Hypophosphorous acid and hypophosphites [H2PO(OH) and H2PO2-J

513Phosphorous acid and phosphites [HPO(OH)2 and HP032- ]

514Hypophosphoric acid (H4P206) and hypophosphates

515Other lower oxoacids of phosphorus

516The phosphoric acids

516Orthophosphates

523Chain polyphosphates

526Cyclo-polyphosphoric acids and cyclo-polyphosphates

52912.3 .7

Phosphorus-nitrogen compounds

531Cyclophosphazanes

533Phosphazenes

534

PolyphosphazenesApplications

12 .3 .8

Organophosphorus compounds

Chapter 13

Arsenic, Antimony and Bismuth

547

13 .1 Introduction

54713 .2

The Elements

54813.2.1

Abundance, distribution and extraction

54813 .2.2

Atomic and physical properties

55013 .2 .3

Chemical reactivity and group trends

55213 .3

Compounds of Arsenic, Antimony and Bismuth

55413 .3 .1

Intermetallic compounds and alloys

55413 .3 .2

Hydrides of arsenic, antimony and bismuth

55713 .3 .3

Halides and related complexes

558Trihalides, MX3

558Pentahalides, MXS

561Mixed halides and lower halides

563Halide complexes of M111 and Mv

564Oxide halides

57013.3 .4

Oxides and oxo compounds

572Oxo compounds of MIII

573Mixed-valence oxides

576Oxo compounds of MV576

13.3.5

Sulfides and related compounds

57813.3 .6

Metal-metal bonds and clusters

58313.3 .7

Other inorganic compounds

59113.3 .8

Organometallic compounds

592Organoarsenic(III) compounds

593Organoarsenic(V) compounds

594Physiological activity of arsenicals

596Organoantimony and organobismuth compounds

596

Chapter 14

Oxygen

60014 .1

The Element14 .1 .1 Introduction14 .1 .2 Occurrence14 .1 .3 Preparation14 .1 .4

Atomic and physical properties14 .1 .5

Other forms of oxygenOzoneAtomic oxygen

14.1 .6

Chemical properties of dioxygen, OZ14.2

Compounds of Oxygen14.2 .1

Coordination chemistry : dioxygen as a ligand14.2 .2 Water

IntroductionDistribution and availabilityPhysical properties and structureWater of crystallization, aquo complexes and solid hydratesChemical propertiesPolywater

14 .2.3

Hydrogen peroxidePhysical propertiesChemical properties

14 .2 .4

Oxygen fluorides14 .2.5 Oxides

Various methods of classificationNonstoichiometry

536542542

600600602603604607607611612615615620620621623625627632633633634638640640642

Chapter 15

Sulfur

64515 .1

The Element

64515.1 .1 Introduction

64515.1 .2

Abundance and distribution

64715.1 .3

Production and uses of elemental sulfur

64915.1 .4

Allotropes of sulfur

65215.1 .5

Atomic and physical properties

66115.1 .6

Chemical reactivity

662Polyatomic sulfur cations

664Sulfur as a ligand

665Other ligands containing sulfur as donor atom

67315.2

Compounds of Sulfur

67615.2 .1

Sulfides of the metallic elements

676General considerations

676Structural chemistry of metal sulfides

679Anionic polysulfides

68115.2 .2

Hydrides of sulfur (sulfanes)

68215.2 .3

Halides of sulfur

683Sulfur fluorides

683Chlorides, bromides and iodides of sulfur

68915.2 .4

Oxohalides of sulfur

69315.2 .5

Oxides of sulfur

695Lower oxides

695Sulfur dioxide, S02

698Sulfur dioxide as a ligand

701Sulfur trioxide

703Higher oxides

70415.2 .6

Oxoacids of sulfur

706Sulfuric acid, H2SO4

710Peroxosulfuric acids, H2SO5 and H2S208

712Thiosulfuric acid, H2S203

714Dithionic acid, H2S206

715Polythionic acids, H2S"O6

716Sulfurous acid, H2SO3

717Disulfurous acid, H2S205

720Dithionous acid, H2S204

72015.2 .7

Sulfur-nitrogen compounds

721Binary sulfur nitrides

722Sulfur-nitrogen cations and anions

730Sulfur imides, S8- �(NH) �

735Other cyclic sulfur-nitrogen compounds

736Sulfur-nitrogen-halogen compounds

736Sulfur-nitrogen-oxygen compounds

Chapter 16

Selenium, Tellurium and Polonium 74716 .1

The Elements

74716.1 .1

Introduction: history, abundance, distribution

74716.1 .2

Production and uses of the elements

74816.1 .3 Allotropy

75116.1 .4

Atomic and physical properties

75316.1 .5

Chemical reactivity and trends

75416.1 .6

Polyatomic cations, M,r"}

75916.1 .7

Polyatomic anions, Mx2-

76216.2

Compounds of Selenium, Tellurium and Polonium

76516.2 .1

Selenides, tellurides and polonides

76516.2.2 Hydrides

76616.2 .3 Halides

767Lower halides

768Tetrahalides

772

xii

Contents

HexahalidesHalide complexes

16 .2 .4

Oxohalides and pseudohalides16 .2 .5 Oxides16 .2 .6

Hydroxides and oxoacids16 .2 .7

Other inorganic compounds16 .2 .8 Organo-compounds

775776777779781783786

Chapter 17

The Halogens: Fluorine, Chlorine, Bromine, Iodine and

789Astatine

17 .1

The Elements

78917 .1 .1 Introduction

789Fluorine

789Chlorine

792Bromine

793Iodine

794Astatine

79417 .1 .2

Abundance and distribution

79517 .1 .3

Production and uses of the elements

79617 .1 .4

Atomic and physical properties

80017 .1 .5

Chemical reactivity and trends

804General reactivity and stereochemistry

804Solutions and charge-transfer complexes

80617.2

Compounds of Fluorine, Chlorine, Bromine and Iodine

80917 .2 .1

Hydrogen halides, HX

809Preparation and uses

809Physical properties of the hydrogen halides

812Chemical reactivity of the hydrogen halides

813The hydrogen halides as nonaqueous solvents

81617 .2 .2

Halides of the elements

819Fluorides

820Chlorides, bromides and iodides

82117.2 .3

Interhalogen compounds

824Diatomic interhalogens, XY

824Tetra-atomic interhalogens, XY3

828Hexa-atomic and octa-atomic interhalogens, XFS and IFS

83217.2.4

Polyhalide anions

83517.2.5

Polyhalonium cations XYZ� +

83917.2.6

Halogen cations

84217.2 .7

Oxides of chlorine, bromine and iodine

844Oxides of chlorine

844Oxides of bromine

850Oxides of iodine

85117.2 .8

Oxoacids and oxoacid salts

853General considerations

853Hypohalous acids, HOX, and hypohalites, XO-

856Halous acids, HOXO, and halites, XOZ-

859Halic acids, HOXOZ, and halates, X03-

862Perhalic acid and perhalates

865Perchloric acid and perchlorates

865Perbromic acid and perbromates

871Periodic acids and periodates

87217.2.9

Halogen oxide fluorides and related compounds

875Chlorine oxide fluorides

875Bromine oxide fluorides

880Iodine oxide fluorides

88117.2.10 Halogen derivatives of oxoacids

88317.3

The Chemistry of Astatine885

Contents

xiii

Chapter 18

The Noble Gases: Helium, Neon, Argon, Krypton, Xenon

888and Radon18 .1 Introduction18 .2

The Elements18 .2 .1

Distribution, production and uses18 .2 .2

Atomic and physical properties of the elements18 .3

Chemistry of the Noble Gases18 .3 .1 Clathrates18 .3 .2

Compounds of xenon18 .3 .3

Compounds of other noble gases

888889889890892893893903

Chapter 19

Coordination and Organometallic Compounds

90519.1 Introduction

90519.2

Types of Ligand

90619.3

Stability of Coordination Compounds

90819.4

The Various Coordination Numbers

91219.5 Isomerism

918Conformational isomerism

918Geometrical isomerism

919Optical isomerism

919Ionization isomerism

920Linkage isomerism

920Coordination isomerism

920Polymerization isomerism

921Ligand isomerism

92119.6

The Coordinate Bond

92119.7

Organometallic Compounds

92419.7 .1

Monohapto ligands

92519.7 .2

Dihapto ligands

93019.7 .3

Trihapto ligands

93319.7 .4

Tetrahapto ligands

93519.7 .5

Pentahapto ligands

93719.7 .6

Hexahapto ligands

94019.7 .7

Heptahapto and octahapto ligands

941

Chapter 20

Scandium, Yttrium, Lanthanum and Actinium

94420 .1 Introduction

94420.2

The Elements

94520.2 .1

Terrestrial abundance and distribution

94520.2.2

Preparation and uses of the metals

94520.2.3

Properties of the elements

94620.2.4

Chemical reactivity and trends

94820.3

Compounds of Scandium, Yttrium, Lanthanum and Actinium

94920.3 .1

Simple compounds

94920.3 .2 Complexes

95020.3 .3

Organometallic compounds

953

Chapter 21

Titanium, Zirconium and Hafnium

95421 .1 Introduction

95421 .2

The Elements

95521 .2 .1

Terrestrial abundance and distribution

95521 .2 .2

Preparation and uses of the metals

95521 .2 .3

Properties of the elements

95621 .2 .4

Chemical reactivity and trends

95821 .3

Compounds of Titanium, Zirconium and Hafnium

96121 .3 .1

Oxides and sulfides

961

XIV Contents

21 .3 .2

Mixed (or. complex) oxides21 .3 .3 Halides21.3 .4

Compounds with oxoanions21.3 .5 Complexes

Oxidation state IV (do)Oxidation state III (d')Lower oxidation states

21 .3 .6

Organometallic compounds

Chapter 22

Vanadium, Niobium and Tantalum22 .1 Introduction

97622.2

The Elements

97722.2 .1

Terrestrial abundance and distribution

97722.2 .2

Preparation and uses of the metals

97722.2.3

Atomic and physical properties of the elements

97822.2 .4

Chemical reactivity and trends

97922.3

Compounds of Vanadium, Niobium and Tantalum

98122.3 .1 Oxides

98122.3 .2 Polymetallates

98322.3 .3

Sulfides, selenides and tellurides

98722.3 .4

Halides and oxohalides

98822.3 .5

Compounds with oxoanions

99322.3 .6 Complexes

994Oxidation state V (do)

994Oxidation state IV (d')Oxidation state III (d2)

994Oxidation state II (d3)

99622.3 .7

The biochemistry of vanadium

99822.3 .8

Organometallic compounds

999999

Chapter 23

Chromium, Molybdenum and Tungsten

100223 .1 Introduction23.2

The Elements23 .2 .1

Terrestrial abundance and distribution23 .2 .2

Preparation and uses of the metals23 .2 .3

Properties of the elements23 .2 .4

Chemical reactivity and trends23.3

Compounds of Chromium, Molybdenum and Tungsten23 .3.1 Oxides23 .3 .2 Isopolymetallates23 .3 .3 Heteropolymetallates23 .3 .4

Tungsten and molybdenum bronzes23 .3 .5

Sulfides, selenides and tellurides23 .3 .6

Halides and oxohalides23 .3 .7

Complexes of chromium, molybdenum and tungstenOxidation state VI (do)Oxidation state V (dl)Oxidation state IV (d 2 )Oxidation state III (d3 )Oxidation state II (d4 )

23 .3 .8

Biological activity and nitrogen fixation23 .3 .9

Organometallic compounds

Chapter 24

Manganese, Technetium and Rhenium24 .1 Introduction24 .2

The Elements

962964966967967969971972

976

100210031003100310041005100710071009101310161017101910231023102410251027103110351037

104010401041

Contents

xv

24.2 .1

Terrestrial abundance and distribution

104124.2 .2

Preparation and uses of the metals

104124.2.3

Properties of the elements

104324.2 .4

Chemical reactivity and trends

104424.3

Compounds of Manganese, Technetium and Rhenium

104524.3 .1

Oxides and chalcogenides

104524.3 .2 Oxcanions

104924.3 .3

Halides and oxohalides

105124.3 .4

Complexes of manganese, technetium and rhenium

1054Oxidation state VII (dO)

1054Oxidation state VI (d')

1055Oxidation state V (d2 )

1055Oxidation state IV (d3 )

1056Oxidation state III (d 4 )

1057Oxidation state II (d 5 )

1058Lower oxidation states

106124.3 .5

The biochemistry of manganese

106124.3 .6

Organometallic compounds

1062

Chapter 25

Iron, Ruthenium and Osmium 107025 .1 Introduction

107025.2

The Elements Iron, Ruthenium and Osmium

107125.2 .1

Terrestrial abundance and distribution

107125.2 .2

Preparation and uses of the elements

107125.2 .3

Properties of the elements

107425.2 .4

Chemical reactivity and trends

107525.3

Compounds of Iron, Ruthenium and Osmium

107925.3 .1

Oxides and other chalcogenides

107925.3 .2

Mixed metal oxides and oxoanions

108125.3.3

Halides and oxohalides

108225.3 .4 Complexes

1085Oxidation state VIII (dO)

1085Oxidation state VII (d')

1085Oxidation state VI (d2 )

1085Oxidation state V (d 3 )

1086Oxidation state IV (d4 )

1086Oxidation state III (d 5 )

1088Oxidation state II (db)

1091Mixed valence compounds of ruthenium

1097Lower oxidation states

109825.3 .5

The biochemistry of iron

1098Haemoglobin and myoglobin

1099Cytochromes

1101Iron-sulfur proteins

110225.3 .6

Organometallic compounds

1104Carbonyls

1104Carbonyl hydrides and carbonylate anions

1105Carbonyl halides and other substituted carbonyls

1108Ferrocene and other cyclopentadienyls

1109

Chapter 26

Cobalt, Rhodium and Iridium

111326 .1 Introduction

111326.2

The Elements

111326.2 .1

Terrestrial abundance and distribution

111326.2 .2

Preparation and uses of the elements

111426.2 .3

Properties of the elements

111526.2 .4

Chemical reactivity and trends

111626.3

Compounds of Cobalt, Rhodium and Iridium

1117

XVI

26.3 .1

Oxides and sulfides26.3 .2 Halides26 .3 .3 Complexes

Oxidation state IV (ds)Oxidation state 111 (db)Oxidation state II (d7 )Oxidation state I (d8 )Lower oxidation states

26.3 .4

The biochemistry of cobalt26.3 .5

Organometallic compoundsCarbonylsCyclopentadienyls

Contents

Chapter 27

Nickel, Palladium and Platinum27 .1 Introduction27 .2

The Elements27 .2 .1

Terrestrial abundance and distribution27.2.2

Preparation and uses of the elements27.2.3

Properties of the elements27.2.4

Chemical reactivity and trends27 .3

Compounds of Nickel, Palladium and Platinum27 .3 .1

The Pd/H2 system27 .3 .2

Oxides and chalcogenides27.3 .3 Halides27.3 .4 Complexes

Oxidation state IV (db)Oxidation state III (d7 )Oxidation state II (d8 )Oxidation state I (d9 )Oxidation state 0 (d 10 )

27 .3 .5

The biochemistry of nickel27 .3 .6

Organometallic compoundsor-Bonded compoundsCarbonylsCyclopentadienylsAlkene and alkyne complexesn-Allylic complexes

111711191121112111221129113311371138113911401143

1144

11441145114511451148114911501150115111521154115411551156116611661167116711671168117011701171

Chapter 28

Copper, Silver and Gold

117328 .1 Introduction28.2

The Elements 1173117428.2.1

Terrestrial abundance and distribution

1 17428.2.2

Preparation and uses of the elements

117428.2.3

Atomic and physical properties of the elements

117628.2.4

Chemical reactivity and trends

117728.3

Compounds of Copper, Silver and Gold

118028.3 .1

Oxides and sulfides

118128.3 .2

High temperature superconductors

118228.3 .3 Halides118328 .3 .4 Photography

118528.3 .5 Complexes1187Oxidation state III (d$)

1187Oxidation state II (d9)

1189Electronic spectra and magnetic properties of copper(II)

1193Oxidation state I (dto) 1194Gold cluster compounds

119728.3 .6

Biochemistry of copper

119728.3 .7

Organometallic compounds

1199

Chapter 29

Zinc, Cadmium and Mercury

Contents

29 .1 Introduction29 .2 The Elements

29 .2 .1

Terrestrial abundance and distribution29 .2 .2

Preparation and uses of the elements29 .2 .3

Properties of the elements29 .2 .4

Chemical reactivity and trends29 .3

Compounds of Zinc, Cadmium and Mercury29 .3 .1

Oxides and chalcogenides29 .3 .2 Halides29 .3 .3 Mercury(I)

Polycations of mercury29 .3 .4

Zinc(II) and cadmium(II)29 .3 .5 Mercury(II)

Hgit -N compoundsHgtt-S compoundsCluster compounds involving mercury

29.3 .6

Organometallic compounds29.3 .7

Biological and environmental importance

Chapter 30

The Lanthanide Elements (Z - 58-71)

122730.1 Introduction30.2

The Elements30.2 .1

Terrestrial abundance and distribution30.2 .2

Preparation and uses of the elements30.2 .3

Properties of the elements30.2 .4

Chemical reactivity and trends30.3

Compounds of the Lanthanides30.3 .1

Oxides and chalcogenides30.3 .2 Halides30.3.3

Magnetic and spectroscopic properties30.3 .4 Complexes

Oxidation state IVOxidation state IIIOxidation state II

30 .3.5

Organometallic compoundsCyclopentadienides and related compoundsAlkyls and aryls

xtrü

1201120112021202120212031205120812081211121312141215121712181220122012211224

12271229122912301232123512381238124012421244124412451248124812481249

Chapter 31

The Actinide and Transactinide Elements (Z - 90-112)

125031 .1 Introduction

1250Superheavy elements

125331 .2

The Actinide Elements

125331 .2.1

Terrestrial abundance and distribution

125331 .2.2

Preparation and uses of the actinide elements

1255Nuclear reactors and atomic energy

1256Nuclear fuel reprocessing

126031 .2 .3

Properties of the actinide elements

126231 .2 .4

Chemical reactivity and trends

126431 .3

Compounds of the Actinides

126731 .3 .1

Oxides and chalcogenides of the actinides

126831 .3 .2

Mixed metal oxides

126931 .3 .3

Halides of the actinide elements

126931 .3 .4

Magnetic and spectroscopic properties

127231 .3 .5

Complexes of the actinide elements

1273Oxidation state VII

1273Oxidation state VI

1273Oxidation state V

1274Oxidation state IV

1275

xviii

Contents

Oxidation state 111

1277Oxidation state 11

127831 .3 .6

Organometallic compounds of the actinides

127831 .4

The Transactinide Elements

128031 .4 .1 Introduction

128031 .4 .2 Element 104

128131 .4 .3 Element 105

128231 .4 .4 Element 106

128231 .4 .5

Elements 107, 108 and 109

128331 .4.6 Elements 110, 111 and 112

1283

Appendix 1

Atomic Orbitals

Appendix 2

Symmetry Elements, Symmetry Operations and Point GroupsAppendix 3

Some Non-SI Units

Appendix 4

Abundance of Elements in Crustal RocksAppendix 5

Effective Ionic RadiiAppendix 6

Nobel Prize for Chemistry

Appendix 7

Nobel Prize for PhysicsIndex

1285

1290

1293

1294

1295

1296

1300

1305